dc.contributor.author
Aguado-Ullate, Sonia
dc.contributor.author
Baker, John A.
dc.contributor.author
González-González, Vanessa
dc.contributor.author
Müller, Christian
dc.contributor.author
Hirst, Jonathan D.
dc.contributor.author
Carbó, Jorge J.
dc.date.accessioned
2018-06-08T04:06:22Z
dc.date.available
2014-10-21T08:27:15.905Z
dc.identifier.uri
https://refubium.fu-berlin.de/handle/fub188/16585
dc.identifier.uri
http://dx.doi.org/10.17169/refubium-20766
dc.description.abstract
The factors governing the activity in Rh-catalyzed hydroformylation were
investigated using a set of computational tools. We performed DFT calculations
on the phosphinine-modified Rh catalyst [HRh(CO)3(PC5H2R3)] and compared it to
the phosphane-modified HRh(CO)3(PR3) and HRh(CO)2(PR3)2 complexes. The
π-acceptor phosphinine ligand coordinates preferentially at the equatorial
site of the pentacoordinated Rh complex with the heterocycle perpendicular to
the equatorial plane, although the ligand freely rotates around the Rh–P bond.
The overall energy barrier can be divided into the following contributions:
alkene complex formation, alkene rotation and alkene insertion. In the absence
of steric effects (model systems), the overall barrier correlates with the
computed barrier for alkene rotation. This proves that π-acceptor ligands
reduce back-donation to the alkene, leading to a lower rotational barrier and,
consequently, to a higher activity. The Rh–P donor–acceptor interactions were
quantified using a modified version of energy decomposition analysis (EDA). In
Rh–phosphinine systems, the efficient directionality of the π-back-donation,
rather than the overall acceptor ability, is responsible for the high
catalytic activity. Introducing steric effects increases the energy required
to coordinate the alkene, increasing the overall barrier. The factors
governing the activity in Rh–monophosphane catalysts seem to be related to
those derived for Rh–diphosphane during the development of a QSAR model
(Catal. Sci. Technol. 2012, 2, 1694). To investigate whether the findings for
mono- can be extrapolated to diphosphane ligands, we re-examined our previous
QSAR model using the Topological Maximum Cross Correlation (TMACC) method
based on easy-to-interpret 2D-descriptors. The TMACC descriptors highlight
heteroatoms close to phosphorus as activity-increasing atoms, whereas highly
substituted carbon atom groups are highlighted as activity-decreasing groups.
en
dc.rights.uri
http://www.rsc.org/AboutUs/Copyright/Authordeposition.asp
dc.subject.ddc
500 Naturwissenschaften und Mathematik::540 Chemie
dc.title
A theoretical study of the activity in Rh-catalysed hydroformylation
dc.type
Wissenschaftlicher Artikel
dcterms.bibliographicCitation
Catalysis Science & Technology. - 4 (2014), 4, S. 979-987
dc.title.subtitle
the origin of the enhanced activity of the π-acceptor phosphinine ligand
dcterms.bibliographicCitation.doi
10.1039/C3CY00956D
dcterms.bibliographicCitation.url
http://xlink.rsc.org/?DOI=c3cy00956d
refubium.affiliation
Biologie, Chemie, Pharmazie
de
refubium.mycore.fudocsId
FUDOCS_document_000000021176
refubium.resourceType.isindependentpub
no
refubium.mycore.derivateId
FUDOCS_derivate_000000004069
dcterms.accessRights.openaire
open access
dcterms.isPartOf.issn
2044-4753